Additions of enantiopure alpha-sulfinyl carbanions to (S)-N-sulfinimines: asymmetric synthesis of beta-amino sulfoxides and beta-alphamino alcohols

The addition of the lithium anions derived from (R)- and (S)-methyl and -ethyl p-tolyl sulfoxides to (S)-N-benzylidene-p-toluenesulfinamide provides an easy access route to enantiomerically pure beta-(N-sulfinyl)amino sulfoxides. Stereoselectivity can be achieved when the configurations at the sulfur atoms of the two reagents are opposite (matched pair), thus resulting in only one diastereoisomer, even for the case in which two new chiral centers are created. The N-sulfinyl group primarily controls the configuration of the carbon bonded to the nitrogen, whereas the configuration of the alpha-sulfinyl carbanion seems to be responsible for the level of asymmetric induction, as well as for the configuration of the new stereogenic C-SO carbon in the reactions with ethyl p-tolyl sulfoxides. An efficient method for transforming the obtained beta-(N-sulfinyl)amino sulfoxides into optically pure beta-amino alcohols, based on the stereoselective non-oxidative Pummerer reaction, is also reported.     

Measurements by microdialysis of free tissue concentrations of propranolol.

To determine the free concentration of a drug (propranolol) in the interstitial space in humans in vivo, seven male students were investigated by microdialysis of the periumbilical subcutaneous tissue. The microdialysis catheters were calibrated in vivo and the propranolol concentration was determined by high-performance liquid chromatography. Ten hours after intake of 80 mg of propranolol, the total plasma and free interstitial propranolol concentrations were 80 +/- 43 and 7 +/- 2 nM, respectively. After a second dose, maximum concentration was reached after 80 +/- 10 min and 98 +/- 12 min, in plasma, and the concentrations in the interstitial water were 594 +/- 138 and 27 +/- 7 nM, respectively. In a second study, microdialysis was performed on the left ventricular wall in six pigs receiving an intravenous injection of 5 mg of propranolol followed by a constant propranolol infusion for 40 min (5 mg propranolol per h). The maximum concentrations of propranolol were 97 +/- 29 and 6 +/- 2 nM in plasma and in interstitial water, respectively. The data suggest that microdialysis is a useful tool for recording the free concentrations of a drug in the interstitial space.     

Soliton experiments in stimulated Raman scattering

Experimental observations of solitons in stimulated Raman scattering are reported. Soliton formation resulted from the introduction of a phase shift in the incident Stokes beam as predicted by theory. Pulse sharpening and retardation on propagation in the Raman medium have been observed along with amplitude diminution. The first two features were predicted and the third was not. Spontaneous soliton formation has been observed in the absense of any amplitude modulation or apparent phase shift in the optical fields, indicating that additional sets of initial conditions may result in soliton formation.Work performed under the auspices of the U.S. Department of Energy.     

(Z)-3-p-tolylsulfinylacrylonitrile as a chiral dienophile: diels-alder reactions with furan and acyclic dienes

The behavior of (Z)-3-p-tolylsulfinylacrylonitrile (1) as a chiral dienophile has been evaluated from its reactions with furan and acyclic dienes. Electrostatic interactions of the cyano group with the sulfinyl one restrict the conformational mobility around the C-S bond, thus controlling the pi-facial selectivity, which is almost complete in all cases, the approach of the diene from the less-hindered face of the dienophile (that bearing the lone electron pair) in the predominant rotamer being the favored one. The regioselectivity is also completely controlled by the cyano group. Additionally, the reactivity of compound 1 as well as its endo-selectivity are both higher than those observed for the corresponding (Z)-3-sulfinylacrylates, thus proving the potential of sulfinylnitriles as chiral dienophiles.     

High-conversion-efficiency, diode-pumped continuous-wave Raman laser

We demonstrate a diode-pumped cw Raman laser in H(2) with photon-conversion efficiency of (66+/-8)%. Pumped by an injection-locked diode laser at 792 nm, the Stokes laser produces a peak output power of ~16mW at 1180 nm. Accompanying the high Stokes power are deviations from the existing theory, which are believed to be caused by the thermal-lensing effect of the Raman gas.     

Spin-singlet clusters in the ladder compound NaV2O5

The space group of alpha(')-NaV2O5 turns below T(c) = 34 K from Pmmn with all V sites equivalent, into Fmm2 with three independent vanadium sites per layer. This is incompatible with models of charge ordering into V4+ and V5+. Our structure determination indicates that the phase transition consists of a charge ordering with three distinct valence states, formally V4+, V4.5+, and V5+. The singlet formation is not associated with dimerization on the spin ladder, but with the formation of spin clusters. Finally, we ascribe the quadrupling of the c axis to the large polarizability of the V2O5 skeleton.     

Widely tunable continuous-wave Raman laser in diatomic hydrogen pumped by an external-cavity diode laser

What is to the authors' knowledge the first experimental demonstration of a nonresonant cw Raman laser pumped by a tunable external-cavity diode laser (ECDL) is presented. The ECDL is phase-frequency locked to a high-finesse Raman laser cavity containing diatomic hydrogen (H(2)) by the Pound-Drever-Hall locking technique. The Stokes lasing threshold occurs at a pump power of 400 +/- 30 muW, and a maximum photon conversion efficiency of 12.0 +/- 1.3% is achieved at 1.6 mW of pump power. A 40-nm tuning range of the cw Stokes emission, 1174-1214 nm, is obtained by tuning of the wavelength of the ECDL pump source.